1 INTRODUCTION

1.1 SCOPE AND OBJECTIVES

A small number of viable options are presently available for the bleaching of wood pulp (delignification and brightening) during the manufacture of pulp and paper. The use of chlorine dioxide (ClO₂) in the bleaching process has largely superceded the earlier use of Cl₂, or elemental chlorine, in the majority of North American pulp mills: It was discovered over a decade ago that the previous widespread use of Cl₂ contributed to the production and subsequent release to the environment of specific forms of potentially deleterious and highly persistent chlorinated organic contaminants, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

The environmental risks and benefits associated with the virtual elimination of Cl₂ in pulp and paper manufacture, and substitution during bleaching with ClO₂ have been formally examined by many scientists; see for example papers by Axegård et al.(1993), Berry et al.(1991), Carey et al.(1993), Luthe et al.(1992), Munkittrick et al.(1996), Södergren (1989), Solomon et al.(1993), and Tana and Lehtinien (1996). In particular, Solomon et al.(1993) conducted a review and risk assessment of the chemistry and biological impacts associated with a 70% to 100% substitution of elemental chlorine with ClO₂ at the request of the Alliance of Environmental Technologies.

Major conclusions from that review are as follows:

• The reaction of lignin with ClO₂ occurs by different chemical processes than the reaction of Cl₂ with lignin. Substitution of Cl₂ by ClO₂ results in great reduction in production of highly chlorinated organic byproducts, (five to ten-fold less) and even greater reductions in dioxins and furans. This has been widely observed in effluent monitoring data.

• Much of the chlorinated organic material released in effluent from bleach kraft pulp mills, and which constitutes the major portion of "Adsorbable Organohalogens" (AOX) or "Extractable Organohalogens" (EOX), is water soluble with very limited lipophilicity, and has little if any tendency to bioaccumulate in aquatic food webs. A clear distinction is required, therefore, between different kinds of organochlorines.

• Toxicity test results for compounds found in final (treated) effluent from pulp mill employing a high degree of ClO₂ substitution do not lead to the expectation of toxicity in receiving waters typical of North American mill operations.

• The weight of evidence overwhelmingly indicated that a high rate of substitution of Cl₂ by ClO₂ will result in reductions in the quantities of organochlorines produced, degree of chlorination in individual molecules, degree of environmental persistence, potential for bioaccumulation and food web transfer, potential toxicity, and adverse ecological effects.

• Finally, the Panel concluded that, pulp mills employing 100% ClO₂ substitution, employing secondary treatment, and discharging into receiving waters with dilution factors typical of most North American mills present an insignificant risk to the environment from organochlorine compounds.

In the same review (Solomon et al.,1993), a number of areas of uncertainty based on the state of knowledge up to 1993 were also identified. In particular, it was concluded that -

• More knowledge was required of the variability in concentrations of organochlorines in biologically treated effluents from mills using high chlorine dioxide substitution, and of whole effluent toxicity (either as acute lethality or measured through sub-acute effects).

• The substances responsible for MFO induction and plasma steroid reduction in fish exposed to biologically treated pulp mill effluents from mills with and without any form of bleaching had not been identified.

• The risks from substances present in effluents produced from mills using "chlorine free" bleaching techniques had not been formally examined.

• More identification and quantification were required of organochlorine compounds in effluent from mills using high chlorine dioxide substitution.

• The sublethal responses in fish at the population level required further investigation.

Following completion of the 1993 review (Solomon et al.,1993), some interest groups have expressed the concern that replacement of Cl₂ by ClO₂ in the bleaching of pulp -- while responsible for a reduction in the production rate of organochlorine byproducts -- has not curtailed their production completely. Nor, according to some, can bioaccumulation of organochlorines from effluent for pulp mills using 100% ClO₂ substitution be ruled out. One of the major points of contention between the most polarized of the factions is whether 100% ClO₂ substitution has resulted in "only marginal environmental improvements", or whether such substitution is sufficient, and when coupled with effective secondary treatment of effluent represents an example of the "best available technology" for pulp and paper production.

Four years have elapsed since the 1993 review -- a period in which the actual monitoring data for pulp mills employing 100% ClO₂ substitution has more than doubled. Considerable additional research has been completed on the fate and effects of pulp and paper mill effluent. This review builds on the content of the previous report (Solomon et al.,1993). It critically evaluates the previous conclusions, and addresses the key questions above along with other issues that have recently been identified as of potential importance. Like the previous review, this report is focused on the effects of pulp mill effluents in the aquatic ecosystem (including possible effects on wildlife via bioaccumulation through the food chain). It specifically excludes air emissions and other environmental impacts external to the mill, such as those associated with production of wood and the impacts of products exported from the mill.

1.2 REVIEW FRAMEWORK

Inherent within an assessment of the possible environmental risks associated with pulp and paper operations that utilize 100% ClO₂ substitution during bleaching are two separate questions:

• What are the risks attributable to the additive or non additive components associated with all aspects of mill operations that result from the final release to the aquatic environment of pulp mill effluents using 100% ClO₂ substitution?

• and, what are the specific risks, if any, contributed by the use of ClO₂ as opposed to other factors in pulp and paper production?

Both questions are directly relevant to understanding the larger environmental consequences of pulp and paper mill aqueous discharges; however, the second question is the one which is most directly relevant to risk management efforts centered around environmentally persistent organochlorines. We have attempted to address both questions here, and have endeavored to distinguish between the two issues.

It is also possible, although often more difficult, to compare the relative environmental risks of two or more operating practices. For example, implicit within an assessment of the risk of 100% ClO₂ substitution for Cl₂ is an assessment of the relative risks of bleaching using elemental chlorine versus chlorine dioxide. It is important to note that this document is not intended to provide a relative comparison between the risks associated with broadly different pulp and paper practices, such as the use of 100% ClO₂ substitution during bleaching (commonly referred to as "elemental chlorine free", or ECF bleaching) versus totally chlorine free, or TCF bleaching.

A number of regulatory jurisdictions have begun to implement environmental risk assessment processes based on set frameworks. Environment Canada has developed a framework similar to that used in the U.S. Environmental Protection Agency (U.S. EPA, 1992) and illustrated in Figure 1 (Environment Canada, 1996). This framework was used as the basis for our assessment.

This process involves the following:

• Characterizing of the possible stressors and their entry into the system including their sources in anthropogenic and natural processes.

• Characterizing the exposures of aquatic biota to these stressors and the fate of these stressors in the receiving environment.

• Characterizing the effects of these stressors on individual organisms at the population and ecosystem level.

• Assessing the risks of these stressors in the receiving environment and relating this to ecological theory and to management practices.

• Considering the implications of background concentrations of chlorinated substances, both natural and anthropogenic, in the environment.

The Framework for risk assessment in the Canadian Environmental Protection Act (CEPA) explicitly recognizes that organisms resident in areas where background concentrations of naturally occurring substances are elevated are likely to be more tolerant to those substances (Environment Canada, 1997). This must be taken into consideration in the risk assessment process. This is particularly important in the risk assessment of substances found in pulp mill effluent and applies to both the naturally occurring substances and chlorinated and other substances produced during bleaching and other processes. Therefore in this assessment, we have also considered the presence of naturally occurring chlorinated and other substances.

As a prerequisite to estimating the risk associated with any input to the environment, one must understand both the major compounds involved (Chapter 2), and the immediate and long-term fate of those compounds. Constituents of pulp mill effluent may be placed in one or more of a small number of categories according to their molecular and, hence, environmental properties. The categorization is, in turn, useful for devising broad predictions regarding the possible extent and mechanism of effects in living organisms (see Chapter 4).

Fig.1 The risk assessment process as proposed for use under CEPA (Environment Canada, 1997)

Ecological risk assessment involves estimating the concentration of potentially deleterious substances (i.e., the exposure) experienced by specific biological populations. This concentration is either measured directly, or estimated from amounts of input from a known source and subsequent redistribution between various environmental compartments. The exposure may then be compared with previously demonstrated exposure-response relationships leading to some toxicological endpoint. Overall, the risk to a population associated with pulp mill effluents will vary according to four factors:

• Physical and chemical properties of compounds in the effluent;

• Input concentrations and rates;

• Environmental redistribution, and

• Environmental concentration-response relationships.

There has been considerable progress since 1993 in characterizing more completely ClO₂-bleaching effluent compounds (Chapter 2). It is also possible to predict, with a quantifiable degree of certainty, the environmental redistribution from physicochemical and environmental properties (e.g., through fugacity-type or other partitioning models). There is, however, insufficient knowledge of concentration-response relationships at the sub-organismic, population, community or ecosystem level (see Chapters 4 and 5) for some of the recently elucidated compounds. It is clear that recent research on biological effects of treated pulp mill effluent has undergone a switch in emphasis with regard to contaminants of concern, to compounds more directly associated with the pulping as opposed to bleaching process. Some of the contaminants of concern are also natural plant products, or may be produced naturally in the aquatic environment